US4989762A - Molten steel pouring nozzle - Google Patents

Molten steel pouring nozzle Download PDF

Info

Publication number
US4989762A
US4989762A US07/460,239 US46023990A US4989762A US 4989762 A US4989762 A US 4989762A US 46023990 A US46023990 A US 46023990A US 4989762 A US4989762 A US 4989762A
Authority
US
United States
Prior art keywords
molten steel
pouring nozzle
steel pouring
refractory
bore
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/460,239
Other languages
English (en)
Inventor
Mitsuru Ando
Takafumi Aoki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akechi Ceramics Co Ltd
Original Assignee
Akechi Ceramics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akechi Ceramics Co Ltd filed Critical Akechi Ceramics Co Ltd
Assigned to AKECHI CERAMICS CO., LTD. reassignment AKECHI CERAMICS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ANDO, MITSURU, AOKI, TAKAFUMI
Application granted granted Critical
Publication of US4989762A publication Critical patent/US4989762A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B22D41/52—Manufacturing or repairing thereof
    • B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/013—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C04B35/103—Refractories from grain sized mixtures containing non-oxide refractory materials, e.g. carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/482—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62665—Flame, plasma or melting treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/768—Perovskite structure ABO3
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/963—Surface properties, e.g. surface roughness
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the present invention relates to a molten steel pouring nozzle which permits effective prevention of reduction or clogging of a bore of the nozzle, through which molten steel flows, when continuously casting an aluminum-killed molten steel containing aluminum.
  • Continuous casting of molten steel is carried out, for example, by pouring molten steel, received from a ladle in a tundish, through a molten steel pouring nozzle secured to the bottom wall of the tundish, into a vertical mold arranged below the molten steel pouring nozzle to form a cast steel strand, and continuously withdrawing the thus formed cast steel strand into a long strand.
  • a nozzle comprising an alumina-graphite refractory is widely used in general.
  • the molten steel pouring nozzle comprising an alumina-graphite refractory has the following problems:
  • non-metallic inclusions such as ⁇ -alumina.
  • the thus produced non-metallic inclusions such as ⁇ -alumina deposit and accumulate onto the surface of the bore of the molten steel pouring nozzle, through which molten steel flows, to clog up the bore, thus making it difficult to achieve stable casting.
  • the non-metallic inclusions such as ⁇ -alumina thus accumulated onto the surface of the bore are peeled off or fall down, and are entangled into the cast steel strand, thus degrading the quality of the cast steel strand.
  • a larger amount of the ejected inert gas causes entanglement of bubbles produced by the inert gas into the cast steel strand, resulting in the production of defects such as pinholes in a steel product after the completion of rolling. This problem is particularly serious in casting of molten steel for a high-quality thin steel sheet.
  • a smaller amount of the ejected inert gas causes, on the other hand, deposition and accumulation of the non-metallic inclusions such as ⁇ -alumina onto the surface of the bore of the molten steel pouring nozzle, thus causing reduction or clogging of the bore.
  • a molten steel pouring nozzle comprising a boron nitride refractory is usually used (hereinafter referred to as the "prior art 2").
  • the molten steel pouring nozzle comprising a boron nitride refractory has a very high manufacturing cost.
  • the function of this nozzle for inhibiting deposition of the non-metallic inclusions such as ⁇ -alumina onto the surface of the bore is not sufficient.
  • boron nitride has a high thermal expansion coefficient.
  • the connection is poor in the interface between the alumina-graphite refractory forming the outer portion of the molten steel pouring nozzle and the boron nitride refractory forming the inner portion of the molten steel pouring nozzle, so that peeloff of the boron nitride refractory from the alumina-graphite refractory during casting of molten steel may make it difficult to accomplish casting.
  • the balance being a refractory aggregate.
  • the above-mentioned refractory aggregate may additionally contain metallic aluminum within the range of from 1 to 15 weight parts relative to 100 weight parts of the refractory aggregate (hereinafter referred to as the "prior art 3").
  • calcium oxide rapidly reacts with the non-metallic inclusions such as ⁇ -alumina produced through reaction of aluminum added as a deoxidizer with oxygen present in molten steel, to produce low-melting-point compounds. Therefore, calcium oxide has a function of preventing the non-metallic inclusions such as ⁇ -alumina from depositing and accumulating onto the surface of the bore.
  • calcium oxide when present alone, violently reacts with water or moisture in the air even at a room temperature to produce calcium hydroxide (Ca(OH) 2 ), which is easily disintegrated and tends to become powdery, thus easily causing degradation of the structure of the molten steel pouring nozzle. Great care is therefore necessary for storing the molten steel pouring nozzle.
  • An object of the present invention is therefore to provide a molten steel pouring nozzle which permits prevention of reduction or clogging of the bore of the nozzle and degradation of the structure of the refractory forming the nozzle economically and for a long period of time without employing a mechanical means such as the ejection of an inert gas.
  • a molten steel pouring nozzle having along the axis thereof a bore through which molten steel flows, characterized in that:
  • At least part of an inner portion of said molten steel pouring nozzle, which inner portion forms said bore, is formed with a refractory consisting essentially of:
  • zirconia clinker comprising cubic zirconia and calcium zirconate:from 40 to 85 wt. %
  • the content of calcium oxide in said zirconia clinker being within the range of from 3 to 35 weight parts relative to 100 weight parts of said zirconia clinker;
  • silica from 1 to 15 wt. %
  • magnesia from 1 to 15 wt. %.
  • FIG. 1 is a schematic vertical sectional view illustrating an embodiment of the molten steel pouring nozzle of the present invention as an immersion nozzle.
  • zirconia clinker having a prescribed particle size is prepared by melting calcium oxide and zirconia in an electric furnace at a temperature of at least 1,600° C., then cooling the resultant melt to solidify same, and then pulverizing the resultant solid.
  • the thus prepared zirconia clinker which comprises cubic zirconia and calcium zirconate (CaO;ZrO 2 ), has a stability similar to stabilized zirconia, and has a low thermal expansion coefficient, and inhibits the violent reaction of calcium oxide with water or moisture in the air, thus preventing degradation of the structure of the molten steel pouring nozzle.
  • At least part of an inner portion of the molten steel pouring nozzle of the present invention, which inner portion forms a bore thereof, is formed with a refractory consisting essentially of:
  • zirconia clinker comprising cubic zirconia and calcium zirconate:from 40 to 85 wt. %
  • the content of calcium oxide in said zirconia clinker being within the range of from 3 to 35 weight parts relative to 100 weight parts of said zirconia clinker;
  • silica from 1 to 15 wt. %
  • magnesia from 1 to 15 wt. %.
  • Zirconia clinker has a low thermal expansion coefficient and an excellent spalling resistance.
  • the content of zirconia clinker is under 40 wt. %, however, the amount of calcium oxide, which is to react with the non-metallic inclusions such as ⁇ -alumina in molten steel, becomes insufficient, thus making it impossible to prevent deposition and accumulation of the non-metallic inclusions such as ⁇ -alumina onto the surface of the bore of the molten steel pouring nozzle.
  • the content of zirconia clinker is over 85 wt. %, on the other hand, the thermal expansion coefficient increases, and the spalling resistance is deteriorated.
  • the content of zirconia clinker should therefore be limited within the range of from 40 to 85 wt. %.
  • Zirconia clinker should preferably have an average particle size of up to 44 ⁇ m to ensure a good surface smoothness of the nozzle.
  • Calcium oxide contained in zirconia clinker reacts with the non-metallic inclusions such as ⁇ -alumina in molten steel to produce the low-melting-point compounds.
  • the content of calcium oxide in zirconia clinker is under 3 weight parts relative to 100 weight parts of zirconia clinker, however, a desired effect as described above cannot be obtained, and the presence of baddeleyite (ZrO 2 ) in zirconia clinker causes degradation of the structure of the molten steel pouring nozzle.
  • Graphite has a function of improving an oxidation resistance as well as a wetting resistance against molten steel of a refractory and increasing a thermal conductivity thereof. Particularly, natural graphite is suitable for obtaining the above-mentioned function. When the content of graphite is under 10 wt. %, however, a desired effect as described above cannot be obtained, and a spalling resistance is poor. When the content of graphite is over 30 wt. %, on the other hand, a corrosion resistance is degraded. The content of graphite should therefore be limited within the range of from 10 to 30 wt. %. Graphite should preferably have an average particle size of up to 500 ⁇ m to improve the above-mentioned functions.
  • Silica has a function of promoting movement of calcium oxide in each particle of zirconia clinker toward the surface of each particle of zirconia clinker and gathering there. Silica has furthermore a function of reducing the thermal expansion coefficient of zirconia clinker and improving the spalling resistance thereof.
  • silica When the content of silica is under 1 wt. %, however, a desired effect as described above cannot be obtained.
  • silica is over 15 wt. %, on the other hand, the structure of the refractory is deteriorated, with a lower corrosion resistance.
  • the content of silica should therefore be limited within the range of from 1 to 15 wt. %. With a view to achieving a satisfactory dispersibility of silica and improving the above-mentioned functions of silica, silica should preferably have an average particle size of up to 20 ⁇ m.
  • Magnesia has, like silica, a function of promoting movement of calcium oxide in each particle of zirconia clinker towards the surface of each particle of zirconia clinker and gathering there.
  • a desired effect as described above cannot be obtained.
  • reaction of magnesia with alumina in molten steel produces spinel (MgO;Al 2 O 3 ), resulting in easier deposition and accumulation of the non-metallic inclusions such as spinel onto the surface of the bore of the molten steel pouring nozzle.
  • magnesia should preferably have an average particle size of up to 20 ⁇ m.
  • the above-mentioned effects of magnesia and silica can be synergetically improved.
  • FIG. 1 is a schematic vertical sectional view illustrating an embodiment of the molten steel pouring nozzle of the present invention as an immersion nozzle.
  • the molten steel pouring nozzle of this embodiment is used as an immersion nozzle which is arranged between a tundish and a vertical mold arranged below the tundish.
  • the molten steel pouring nozzle 4 of the present invention has along the axis thereof a bore 1 through which molten steel flows.
  • An inner portion 2 of the molten steel pouring nozzle 4, which forms the bore 1, is formed with a refractory having the above-mentioned chemical composition.
  • An outer portion 3, which surrounds the inner portion 2, is formed with a refractory, for example, an alumina-graphite refractory which has an excellent erosion resistance against molten steel.
  • a refractory for example, an alumina-graphite refractory which has an excellent erosion resistance against molten steel.
  • phenol resin in the state of powder and liquid in an amount of from 5 to 10 wt. % was added to each of the blended raw materials Nos. 1 to 3 including the above-mentioned zirconia clinker thus prepared, having the chemical compositions within the scope of the present invention as shown in Table 1.
  • Each of these blended raw materials Nos. 1 to 3 with added phenol resin was mixed and kneaded to obtain a kneaded mass.
  • the results are shown in Table 2.
  • each of the samples of the invention Nos. 1 to 3 and the samples for comparison Nos. 4 to 6 having dimensions of 30 mm ⁇ 30 mm ⁇ 250 mm was immersed in molten steel at a temperature of 1,550° C. containing aluminum in an amount within the range of from 0.05 to 0.10 wt. % for 180 minutes to investigate an erosion ratio (%) and an amount of deposition (mm) of the non-metallic inclusions such as ⁇ -alumina.
  • the results are also shown in Table 2.
  • all the samples of the invention Nos. 1 to 3 are excellent in the surface properties, with in addition a low erosion ratio, so that it is possible to avoid deterioration of the structure of the refractory.
  • the samples of the invention Nos. 1 to 3 have furthermore an excellent spalling resistance and have no deposition of the non-metallic inclusions such as ⁇ -alumina, thus permitting effective prevention of reduction or clogging of the bore of the molten steel pouring nozzle.
  • All the samples for comparison Nos. 4 to 6 have in contrast a large amount of deposition of the non-metallic inclusions such as ⁇ -alumina. Particularly, the sample for comparison No.
  • phenol resin in the state of powder and liquid in an amount of from 5 to 10 wt. % was added to each of the blended raw materials Nos. 1 and 3 having the chemical compositions within the scope of the present invention as shown in Table 1.
  • Each of the raw materials Nos. 1 and 3 with added phenol resin was mixed and kneaded to obtain a kneaded mass.
  • each of the thus obtained kneaded masses was used for the inner portion 2 of the molten steel pouring nozzle 4, which inner portion 2 formed the bore 1, and an alumina-graphite refractory was used for the outer portion 3 of the molten steel pouring nozzle 4 so as to surround the above-mentioned inner portion 2.
  • the inner portion 2 and the outer portion 3 were integrally formed by means of the known isostatic pressing under a forming pressure of 1 ton/cm 2 , and then reduction-fired at a temperature within the range of from 1,000° to 1,200° C. to prepare molten steel pouring nozzles as immersion nozzles (hereinafter referred to as the "nozzles of the invention") Nos. 1 and 3.
  • a known molten steel pouring nozzle in which an inert gas was ejected from the surface of the bore of the nozzle toward molten steel flowing through the bore (hereinafter referred to as the "nozzle for comparison"), was provided.
  • the nozzles of the invention Nos. 1 and 3 and the nozzle for comparison were fitted between the tundish and a vertical mold arranged below the tundish, and an aluminum-killed molten steel containing aluminum in an amount within the range of from 0.05 to 0.06 wt. % was continuously cast for 400 minutes, to investigate the state of deposition of the non-metallic inclusions such as ⁇ -alumina for each of the nozzles of the invention Nos. 1 and 3 and the nozzle for comparison.
  • the amount of the non-metallic inclusions such as ⁇ -alumina having deposited onto the surface of the bore each of the nozzles of the invention Nos. 1 and 3 was within the range of from 0 to 2 mm, whereas that in the nozzle for comparison was within the range of from 4 to 12 mm.
  • the molten steel pouring nozzle of the present invention as described above in detail, it is possible to stably prevent reduction or clogging of the bore of the nozzle by the non-metallic inclusions such as ⁇ -alumina for a long period of time without causing degradation of the structure of the refractory.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Compositions Of Oxide Ceramics (AREA)
US07/460,239 1989-02-07 1990-01-02 Molten steel pouring nozzle Expired - Fee Related US4989762A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1028279A JPH02207951A (ja) 1989-02-07 1989-02-07 連続鋳造用ノズルの製造方法
JP1-28279 1989-02-07

Publications (1)

Publication Number Publication Date
US4989762A true US4989762A (en) 1991-02-05

Family

ID=12244157

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/460,239 Expired - Fee Related US4989762A (en) 1989-02-07 1990-01-02 Molten steel pouring nozzle

Country Status (6)

Country Link
US (1) US4989762A (ja)
JP (1) JPH02207951A (ja)
KR (1) KR920005724B1 (ja)
DE (1) DE4003568A1 (ja)
FR (1) FR2642687B1 (ja)
GB (1) GB2227962B (ja)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5086957A (en) * 1990-01-23 1992-02-11 Akechi Ceramics Co., Ltd. Molten steel pouring nozzle
US5151201A (en) * 1988-07-01 1992-09-29 Vesuvius Crucible Company Prevention of erosion and alumina build-up in casting elements
US5244130A (en) * 1992-01-27 1993-09-14 Akechi Ceramics Co., Ltd. Molten steel pouring nozzle
US5335833A (en) * 1992-09-14 1994-08-09 Vesuvius Crucible Company Zirconia graphite slide gate plates
US5370370A (en) * 1993-02-19 1994-12-06 Vesuvius Crucible Company Liner for submerged entry nozzle
US5902511A (en) * 1997-08-07 1999-05-11 North American Refractories Co. Refractory composition for the prevention of alumina clogging
EP0970768A1 (en) * 1998-07-09 2000-01-12 Akechi Ceramics Kabushiki Kaisha A continuous casting nozzle for molten steel
AU730801B2 (en) * 1996-12-05 2001-03-15 Akechi Ceramics Kabushiki Kaisha A continuous casting nozzle for casting molten steel
US6491190B1 (en) 1999-11-22 2002-12-10 Bruce E. Dunworth Permeable refractory nozzle and manufacturing method
US6637629B2 (en) 2000-04-18 2003-10-28 Toshiba Ceramics Co., Ltd. Immersion nozzle
US20060214029A1 (en) * 2003-08-22 2006-09-28 Katsumi Morikawa Immersion nozzle for continuous casting of steel and method for continuous steel casting of steel using the immersion nozzle
CN106470958A (zh) * 2014-07-14 2017-03-01 里弗雷克特里知识产权两合公司 耐火产品、二氧化锆的用途、二氧化锆、用于制造耐火产品的方法和由其制造的耐火产品
CN107073565A (zh) * 2014-10-31 2017-08-18 株式会社Posco 连续铸造用浸渍喷嘴
CN110918970A (zh) * 2019-11-15 2020-03-27 中天钢铁集团有限公司 一种降低硅脱氧钢加工过程断丝率的浸入式水口内衬材料

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07214259A (ja) * 1994-01-25 1995-08-15 Akechi Ceramics Kk 溶鋼の連続鋳造用ノズル
KR100286663B1 (ko) * 1996-12-13 2001-04-16 이구택 티밍래들용 염기성 내화물
WO2011138831A1 (ja) 2010-05-07 2011-11-10 黒崎播磨株式会社 耐火物、その耐火物を使用した連続鋳造用ノズル及びその連続鋳造用ノズルの製造方法、並びにその連続鋳造用ノズルを使用した連続鋳造方法
DE102012003483B3 (de) * 2012-02-21 2013-02-21 Technische Universität Bergakademie Freiberg Thermoschock- und korrosionsbeständiger Keramikwerkstoff auf der Basis von Calciumzirkonat und Verfahren zu seiner Herstellung

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4585485A (en) * 1983-01-24 1986-04-29 Hiroshi Shikano Refractory sliding nozzle plate
US4849383A (en) * 1986-12-24 1989-07-18 Mino Yogyo Company, Ltd. Basic refractory composition

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT247533B (de) * 1964-11-20 1966-06-10 Plansee Metallwerk Behälter zur Aufnahme von Metallschmelzen, insbesondere Eisen- und Stahlschmelzen
JPS591229B2 (ja) * 1978-04-26 1984-01-11 明知耐火煉瓦株式会社 溶鋼の連続鋳造用浸漬ノズル
IT1186695B (it) * 1982-07-05 1987-12-04 Centro Speriment Metallurg Perfezionamento nel colaggio di acciat calmati all'alluminio
FR2533208B1 (fr) * 1982-09-22 1986-08-01 Produits Refractaires Composition refractaire moulable a base de zircone partiellement stabilisee et d'un liant hydraulique alumineux, sa preparation et pieces fabriquees a partir de cette composition
JPS59162174A (ja) * 1983-03-07 1984-09-13 ハリマセラミック株式会社 連続鋳造用ノズルの製造方法
IT1172313B (it) * 1983-07-27 1987-06-18 Centro Speriment Metallurg Perfezionamento negli scaricatori per il colaggio di acciai calmati all'alluminio
AU593102B2 (en) * 1986-05-22 1990-02-01 Foseco International Limited Casting of metals
JP2542585B2 (ja) * 1986-08-08 1996-10-09 東芝セラミツクス株式会社 連続鋳造用浸漬ノズル
DE3627337A1 (de) * 1986-08-12 1988-02-25 Didier Werke Ag Eintauchausguss und verfahren zu seiner herstellung
FR2633611B1 (fr) * 1988-07-01 1991-05-10 Vesuvius France Sa Materiau pour le recouvrement d'organe de coulee

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4585485A (en) * 1983-01-24 1986-04-29 Hiroshi Shikano Refractory sliding nozzle plate
US4849383A (en) * 1986-12-24 1989-07-18 Mino Yogyo Company, Ltd. Basic refractory composition

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5151201A (en) * 1988-07-01 1992-09-29 Vesuvius Crucible Company Prevention of erosion and alumina build-up in casting elements
US5086957A (en) * 1990-01-23 1992-02-11 Akechi Ceramics Co., Ltd. Molten steel pouring nozzle
US5244130A (en) * 1992-01-27 1993-09-14 Akechi Ceramics Co., Ltd. Molten steel pouring nozzle
US5335833A (en) * 1992-09-14 1994-08-09 Vesuvius Crucible Company Zirconia graphite slide gate plates
US5370370A (en) * 1993-02-19 1994-12-06 Vesuvius Crucible Company Liner for submerged entry nozzle
AU730801B2 (en) * 1996-12-05 2001-03-15 Akechi Ceramics Kabushiki Kaisha A continuous casting nozzle for casting molten steel
US5902511A (en) * 1997-08-07 1999-05-11 North American Refractories Co. Refractory composition for the prevention of alumina clogging
EP0970768A1 (en) * 1998-07-09 2000-01-12 Akechi Ceramics Kabushiki Kaisha A continuous casting nozzle for molten steel
US6491190B1 (en) 1999-11-22 2002-12-10 Bruce E. Dunworth Permeable refractory nozzle and manufacturing method
US6637629B2 (en) 2000-04-18 2003-10-28 Toshiba Ceramics Co., Ltd. Immersion nozzle
US20060214029A1 (en) * 2003-08-22 2006-09-28 Katsumi Morikawa Immersion nozzle for continuous casting of steel and method for continuous steel casting of steel using the immersion nozzle
US7275584B2 (en) * 2003-08-22 2007-10-02 Krosakiharima Corporation Immersion nozzle for continuous casting of steel and continuous steel casting method using same
CN106470958A (zh) * 2014-07-14 2017-03-01 里弗雷克特里知识产权两合公司 耐火产品、二氧化锆的用途、二氧化锆、用于制造耐火产品的方法和由其制造的耐火产品
US20170152188A1 (en) * 2014-07-14 2017-06-01 Refractory Intellectual Property Gmbh & Co. Kg Refractory product, use of zirconium dioxide, zirconium dioxide, method for manufacturing a refractory product and a refractory product manufactured therewith
US10000418B2 (en) * 2014-07-14 2018-06-19 Refractory Intellectual Property Gmbh & Co. Kg Refractory product, use of zirconium dioxide, zirconium dioxide, method for manufacturing a refractory product and a refractory product manufactured therewith
CN107073565A (zh) * 2014-10-31 2017-08-18 株式会社Posco 连续铸造用浸渍喷嘴
CN107073565B (zh) * 2014-10-31 2019-05-10 株式会社Posco 连续铸造用浸渍喷嘴
CN110918970A (zh) * 2019-11-15 2020-03-27 中天钢铁集团有限公司 一种降低硅脱氧钢加工过程断丝率的浸入式水口内衬材料

Also Published As

Publication number Publication date
KR920005724B1 (ko) 1992-07-16
JPH0314540B2 (ja) 1991-02-27
DE4003568C2 (ja) 1992-09-10
JPH02207951A (ja) 1990-08-17
FR2642687B1 (fr) 1993-12-31
FR2642687A1 (fr) 1990-08-10
GB9001483D0 (en) 1990-03-21
KR900012709A (ko) 1990-09-01
DE4003568A1 (de) 1990-08-09
GB2227962A (en) 1990-08-15
GB2227962B (en) 1992-12-16

Similar Documents

Publication Publication Date Title
US4989762A (en) Molten steel pouring nozzle
US5083687A (en) Nozzle for continuous casting and method of producing
US4913408A (en) Refractory liner compositions
US5086957A (en) Molten steel pouring nozzle
US5505348A (en) Molten steel pouring nozzle
US5244130A (en) Molten steel pouring nozzle
JPH0839214A (ja) 連続鋳造用ノズル
EP0885674B1 (en) Nozzle for the continuous casting of steel
EP0818259B1 (en) Nozzle for use in continuous casting of steel
US5902511A (en) Refractory composition for the prevention of alumina clogging
US5911900A (en) Continuous casting nozzle for casting molten steel
US6533146B1 (en) Continuous casting nozzle for molten steel
US6637629B2 (en) Immersion nozzle
US5975382A (en) Continuous casting nozzle for casting molten steel
JPH02180753A (ja) 連続鋳造用浸漬ノズルの製造方法
AU746450B2 (en) Continuous casting nozzle
EP0970768B1 (en) A continuous casting nozzle for molten steel
KR100473111B1 (ko) 캐스팅시공용부정형내화물및이것을라이닝한용강용기
WO2000061321A1 (fr) Buse de coulee continue
JPH05228593A (ja) 溶鋼の連続鋳造用ノズル
JPH09201660A (ja) 連続鋳造用ノズル
JPH11320048A (ja) 鋼の連続鋳造用ノズル

Legal Events

Date Code Title Description
AS Assignment

Owner name: AKECHI CERAMICS CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ANDO, MITSURU;AOKI, TAKAFUMI;REEL/FRAME:005210/0513

Effective date: 19891220

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 20030205

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362